Preparation of vitamin compositions



- Patent ed W 4W PREPARATION OF VITAIVIIN COMPOSITIONS Kenneth C. D. Hickman, Rochester, N. Y., as-

signor, by mesne assignments, to Distillation Products, Inc., Rochester, N. Y., a. corporation of Delaware No Drawing.

8 Claims.

This invention pertains to the preparation of therapeutic concentrates by high va cuum distillation of organic oils and is in parts. continuation of my q. S. app1ica-tion 37,751, filed August 24,

It is known that vitamin concentrates can be economically produced by high vacuum distillation of organic oils such as fish oils containing such substances. In generalthe' procedure involves heating the oil, preferably i-n a thin film to distillation temperature under a high vacuum and condensing vaporized molecules upon a condensing surface separated from'the vaporizing zone by substantially unobstructed space. The distance between the vaporizing zone and the condensing surface should preferably be less than about the mean free path of the residual gases present in the distillation chamber. In practice short distances of less than 12 inches, such as to 4 inches are most generally satisfactory.

Pressures of residual gas below 1 mm. and espe cially below .1 mm. such as .005-.001 mm. are usually employed. Y

In carrying out these distillations I have found that free fatty acids are obtained in concentrated form in some of the lower fractions containing vitamins. The fatty acids. are in the main the same as those which were'present in free form prior to the distillation. These materials distill at temperatures below about 170 and especially at about 110-160 C. Considerable amounts of the vitamins distill. at these same temperatures. These mixed distillates have rather low value because of their high acid content and taste.

This invention has for its object to overcome the above dimculties. Another object is to provide an improved process which will yield high vacuum distillates substantially free of fatty acids. A further object is to provide a process for preparing vitamin distillates in improved form, for

instance such that have improved taste and/o1 ingestible qualities. Other objects will appear from the following description.

These and other objects are accomplished in accordance with my invention which, in general, comprises substantial neutralization of the 'free acid contentof the vitamin-containing oil prior to distillation to separate the vitamin content of the oil. This treatment results in the substantial removal of fatty acids and acts to improve the quality of the distillates.

In the following examples and description I have given several of the preferred embodiments of my invention, but'it is to be understood that Application March 15, 1938, Serial No. 196,031

these are given for the purpose of illustration and not as limitations thereof.

The oil, such as "forinstance a fish oil from which the vitamins are to be distilled, is treated with an alkali in amounts suflicient to substantially neutralize free fatty acids contained/there "stantially greater amounts cause decomposition or conversion of vitamin esters into lower boiling undesirable forms as well as loss of valuable V 7' oil. The amount of alkali required canb readily determined by preliminary titration of a small 16 sample of the oil..- I prefer to use aqueous solutions of the alkaline compound, but this is unnecessary since solid alkali can be added, and the oil separated from the solid soaps formed. Alkalies usually employed for neutralization can 20 be used. Examples are sodium, potassium, lithium, calcium, etc. hydroxides; sodium carbonate, ammonium hydroxide, etc., modified alkalies such as the basic silicates, phosphates, sesq'ui carbonates, etc., are also useful. 25

After addition of the alkaline solution, the mixture is agitated until the oil has been thoroughly contacted with the alkali and the acids neutralized. It is desirable, but not essential, to warm the mixture slightly during this period. A

temperature of about 40 C. is satisfactory. This results in an improved soap precipitation and a clearer oil. When the acids have been neutralized the agitation is discontinued and the oil allowed to settle. The oil is then decanted or 35 siphoned from the soaps. It may still retain small amounts of soap in the form of a fine precipitate and it is therefore desirable to filter the oil to directly remove these materials. However this step is not necessary, especially if the mixture is given sufficient time tosettle.

After the above treatment the oil can be directly distilled, preferably after degassing in the usual and known manner. The oil may be washed and/or dried before distillation, but such procedure is not ordinarily necessary. Manifestly the possibility of avoiding these costly and cumbersome steps is a decided advantage.

Operation in this manner will avoid undue loss. of the oil. After decanting a portion of the oil 50 will be retained by the solid soaps and can be recovered therefrom by obvious expedients such as salting out, acidification, gravity separation or centrifuging.

Since the ultimate purpose is the recovery of by other methods.

rancid oil is distilled, odoriferous concentrates are obtained especially in the first fractions. An

using the above in which my invention is carried out to yield 4600 gins. of pollack liver oil having a vitamin A potency of 10,600 units per gram, an acid value of 1.8 and free fatty acid content of .9 percent was heated to 40 C. 9 gms. of caustic soda disassociated. Their removal from the sensitive vitamin concentrates is therefore of increased Removal prior to distillation prevents any possibility of loss due to-this cause either during distillation or subsequent storage.

I 1. The process for a vitamin concentrate from an oil which contains fat soluble solved in 40 cc. of water was added to them ith vitamins including vitamin esters and free unt slow agitation. Agitation was continued the flocculation pointwas reached. The mixture was allowed to settle, the oil siphoned oil" and filtered through a silicious filter bed. 4285 grams of refined oil having a vitamin A potency of 12,200 units per gram and acid value .of .033 was obtained. After degassing this was sub:

Jected to distillation in a small high vacuum still having the vaporizing and condensing surfaces separated by about 1 inch. The following table indicates the course of the distillation and thecharacter of the products.

' distillate fractio n'contasw mmer in combinationmeu tralizdng the free fatty acids, without causing a vitamin. 2. The process for preparinga vitamin constill Weight, Percent Vitamin A Percent Acid O. grams cut potency vitimin A value 136-186 01 28, 600 i. 4 4. 0 186-210 12 as 240, 000 6. 0 1. 80 as 82 170, 000 11. s 98 89 2. i0 100, 000 17. 2 61 286 158 8. 62, 000 18. 8 81 2st 220 5. 10 as, 000 10. 4 as 240 ,211 4.0 10,000 0.4 .16 e 240 261 6. 9 0, 600 4. 7 08 8,150 1, 700 10. 7 .08

The above shows the remarkably low acid value of the vitamin fractions after removing a relatively small preliminary fraction.

Although I have found 'it convenient to describe my invention by reference to particular oils, it is to be understood that it is in no way limited to the treatment of particular substances. Oils containing fat soluble vitamins in Molecular, or high vacuum distillation of vitamin containing oils yields concentrates of vitamins which are vastly superior to thoseproduced However, when 'a particularly acids ordinarily. distilled with these fractions,

they could not have been easily removed by redistillation .which, in any event, would have involved considerable expense and thermal loss. The alkali treatment prior to distillation overcomesthese difiiculties. It also increases the oil from the neutralized fatty acids, and subjecting the oil to distillation by heating it in the form film under a high-vacuum and condensing vitamin molecules upon a condensing surface separated from the film by substantially. unobstructed space.

3. The process for preparing a vitamin con-' centrate from a fish oil which contains vitamins as well as free fatty acids which comprises treating the oil with alkali .sufilcient to neutralize substantially all of the free fatty acid, but insufiicient to appreciably saponify the oil, separating the oil from the soaps thus formed. and subjecting the oil to distillation by heating it in a thin film under a residual gas pressure of a short distance from the heated'film.

4. The process for preparing a vitamin concentrate from a fish oil which contains vitamins as well as free fatty acids which comprises treating the oil with alkali in slight excess to that required to neutralize the free fatty acids, separating the oil from the soaps thus formed, and subjecting the oil to distillation by heating it in a thin film under a residual gas pressure of less than .1 min. and condensing vaporized vitamin molecules upon a-condensing surface separated from the film by a distance of less than about the mean free path of the molecules of residual 888.

5. The process for preparing a vitamin con-.

ii which is devoid of vitamin A activity.-

' alum centrate from a fish oil which contains vitamins 'as well as free fatty acidswhich comprises in combination, treating the oil with a solution of alkali in amounts sumcient to substantially neutralize the free fatty acids, but insufiicient to cause substantial saponiiication of the oil, separating the oil from the resultant soaps and sub- Jectinz ittodistillaticnbyheating it in a thin film under a residual gas pressure of less than about .1 mm. and condensing vaporized molecules upon a condensing surface located at a distance from the heated film of between about '%and4inches.v

6. The process forpreparinz a vitamin'conccntrate from-a fish oil which contains vitamins as well as free fatty acids, which process comprises treating-the oil with an aqueous alkali solution suiiicient to neutralize substantially all of the free fatty acid contained in the oil, but

insuiiicient to appreciably saponiiy the oil, separating the oil from the soap solution and directly subjecting the oil to distillation by heating it in a thin film under a residual gas pressure of less than about .1 mm.. and condensing vaporized vitamin molecules upon a condensing surface located a short distance from the iilm.

mum-n c. D; mamas. 

